Described herein is a composition and method for the formation of a silicon and oxygen containing film. More specifically, described herein is a composition and method for formation of a stoichiometric or a non-stoichiometric silicon oxide film or material at one or more deposition temperatures of about 300° C. or less, or ranging from about 25° C. to about 600° C.
Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic Layer Deposition (PEALD) are processes used to deposit silicon oxide conformal films at low temperatures (<500° C.). In both ALD and PEALD processes, the precursor and reactive gas (such as oxygen or ozone) are separately pulsed in certain number of cycles to form a monolayer of silicon oxide at each cycle. However, silicon oxide deposited at low temperatures using these processes may contain levels of impurities such as, without limitation, nitrogen (N) which may be detrimental in certain semiconductor applications. To remedy this, one possible solution is to increase the deposition temperature to 500° C. or greater. However, at these higher temperatures, conventional precursors employed by semi-conductor industries tend to self-react, thermally decompose, and deposit in a chemical vapor deposition (CVD) mode rather than an ALD mode. The CVD mode deposition has reduced conformality compared to ALD deposition, especially for high aspect ratio structures which are needed in many semiconductor applications. In addition, the CVD mode deposition has less control of film or material thickness than the ALD mode deposition.
The reference article entitled “Some New Alkylaminosilanes,” Abel, E. W. et al., J. Chem. Soc., (1964), Vol. 26, pp. 1528-1530 describes the preparation of various aminosilane compounds such as Me3SiNHBu-iso, Me3SiNHBu-sec, Me3SiN(Pr-iso)2, and Me3SiN(Bu-sec)2 wherein Me=methyl, Bu-sec=sec-butyl, and Pr-iso=isopropyl from the direct interaction of trimethylchlorosilane (Me3SiCl) and the appropriate amine.
The reference article entitled “SiO2 Atomic Layer Deposition Using Tris(dimethylamino)silane and Hydrogen Peroxide Studied by in Situ Transmission FTIR Spectroscopy, Burton, B. B., et al., The Journal of Physical Chemistry (2009), Vol. 113, pp. 8249-57 describes the atomic layer deposition (ALD) of silicon dioxide (SiO2) using a variety of silicon precursors with H2O2 as the oxidant. The silicon precursors were (N,N-dimethylamino)trimethylsilane) (CH3)3SiN(CH3)2, vinyltrimethoxysilane CH2CHSi(OCH3)3, trivinylmethoxysilane (CH2CH)3SiOCH3, tetrakis(dimethylamino)silane Si(N(CH3)2)4, and tris(dimethylamino)silane (TDMAS) SiH(N(CH3)2)3. TDMAS was determined to be the most effective of these precursors. However, additional studies determined that SiH* surface species from TDMAS were difficult to remove using only H2O. Subsequent studies utilized TDMAS and H2O2 as the oxidant and explored SiO2 ALD in the temperature range of 150-550° C. The exposures required for the TDMAS and H2O2 surface reactions to reach completion and were monitored using in situ FTIR spectroscopy. The FTIR vibrational spectra following the TDMAS exposures showed a loss of absorbance for O—H stretching vibrations and a gain of absorbance for C—Hx and Si—H stretching vibrations. The FTIR vibrational spectra following the H2O2 exposures displayed a loss of absorbance for C—Hx and Si—H stretching vibrations and an increase of absorbance for the O—H stretching vibrations. The SiH* surface species were completely removed only at temperatures>450° C. The bulk vibrational modes of SiO2 were observed between 1000-1250 cm−1 and grew progressively with number of TDMAS and H2O2 reaction cycles. Transmission electron microscopy (TEM) was performed after 50 TDMAS and H2O2 reaction cycles on ZrO2 nanoparticles at temperatures between 150-550° C. The film thickness was determined by TEM at each temperature to obtain the SiO2 ALD growth rate. The growth per cycle varied from 0.8 Å/cycle at 150° C. to 1.8 Å/cycle at 550° C. and was correlated with the removal of the SiH* surface species. SiO2 ALD using TDMAS and H2O2 should be valuable for SiO2 ALD at temperatures>450° C.
JP 2010275602 and JP 2010225663 disclose the use of a raw material to form a Si containing thin film such as, silicon oxide, by a chemical vapor deposition (CVD) process at a temperature range of from 300-500° C. The raw material is an organic silicon compound, represented by formula: (a) HSi(CH3)(R1)(NR2R3), wherein, R1 represents NR4R5 or a 1C-5C alkyl group; R2 and R4 each represent a 1C-5C alkyl group or hydrogen atom; and R3 and R5 each represent a 1C-5C alkyl group); or (b) HSiCl(NR1R2)(NR3R4), wherein R1 and R3 independently represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom; and R2 and R4 independently represent an alkyl group having 1 to 4 carbon atoms. The organic silicon compounds contained H—Si bonds.
U.S. Pat. No. 5,424,095 describes a method to reduce the rate of coke formation during the industrial pyrolysis of hydrocarbons, the interior surface of a reactor is coated with a uniform layer of a ceramic material, the layer being deposited by thermal decomposition of a non-alkoxylated organosilicon precursor in the vapor phase, in a steam containing gas atmosphere in order to form oxide ceramics.
U.S. 2012/0291321 describes a PECVD process for forming a high-quality Si carbonitride barrier dielectric film between a dielectric film and a metal interconnect of an integrated circuit substrate, comprising the steps of: providing an integrated circuit substrate having a dielectric film or a metal interconnect; contacting the substrate with a barrier dielectric film precursor comprising: RxRy(NRR′)zSi wherein R, R′, R and R′ are each individually selected from H, linear or branched saturated or unsaturated alkyl, or aromatic group; wherein x+y+z=4; z=1 to 3; but R, R′ cannot both be H; and where z=1 or 2 then each of x and y are at least 1; forming the Si carbonitride barrier dielectric film with C/Si ratio>0.8 and a N/Si ratio>0.2 on the integrated circuit substrate.
U.S. 2013/0295779 describes an atomic layer deposition (ALD) process for forming a silicon oxide film at a deposition temperature>500° C. using silicon precursors having the following formula:R1R2mSi(NR3R4)nXp  I.wherein R1, R2, and R3 are each independently selected from hydrogen, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group; R4 is selected from, a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group, a C3 to C10 alkylsilyl group; wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; and p is 0 to 2 and m+n+p=3; andR1R2mSi(OR3)n(OR4)qXp  II.wherein R1 and R2 are each independently selected from hydrogen, a linear or branched C, to C10 alkyl group, and a C6 to C10 aryl group; R3 and R4 are each independently selected from a linear or branched C1 to C10 alkyl group, and a C6 to C10 aryl group;wherein R3 and R4 are linked to form a cyclic ring structure or R3 and R4 are not linked to form a cyclic ring structure; X is a halide atom selected from the group consisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2 and p is 0 to 2 and m+n+q+p=3
U.S. Pat. No. 7,084,076 discloses a halogenated siloxane such as hexachlorodisiloxane (HCDSO) that is used in conjunction with pyridine as a catalyst for ALD deposition below 500° C. to form silicon dioxide.
U.S. Pat. No. 6,992,019 discloses a method for catalyst-assisted atomic layer deposition (ALD) to form a silicon dioxide layer having superior properties on a semiconductor substrate by using a first reactant component consisting of a silicon compound having at least two silicon atoms, or using a tertiary aliphatic amine as the catalyst component, or both in combination, together with related purging methods and sequencing. The precursor used is hexachlorodisilane. The deposition temperature is between 25-150° C.
WO 2015/0105337 discloses novel trisilyl amine derivatives and a method for formation of silicon containing thin films, wherein the trisilyl amine derivatives are having thermal stability, high volatility, and high reactivity and being present in a liquid state at room temperature and under pressure where handling is possible, may form a high purity silicon containing thin film having excellent physical and electric properties by various deposition methods.
WO 2015/0190749 discloses novel amino-silyl amine compounds, (Me2NSiR3R4)N(SiHR1R2)2 (R1-R4=C1-3 alkyl, C2-3 alkenyl, C2-3 alkynyl, C3-7 cycloalkyl, C6-12 aryl, etc.), and a method of a dielectric film containing Si—N bond. Since the amino-silyl amine compd. according to the present invention, which is a thermally stable and highly volatile compd., may be treated at room temp. and used as a liq. state compd. at room temp. and pressure, the present invention provides a method of a high purity dielectric film containing a Si—N bond even at a low temp. and plasma condition by using at. layer deposition (PEALD).
U.S. Pat. No. 9,245,740 B provides novel amino-silyl amine compounds, a method for preparing the same, and a silicon-containing thin-film using the same, wherein the amino-silyl amine compd. has thermal stability and high volatility and is maintained in a liquid state at room temp. and under a pressure where handling is easy to thereby form a silicon-containing thin-film having high purity and excellent physical and electric properties by various deposition methods.
U.S. 2015/0376211 discloses mono-substituted TSA precursor Si-containing film forming compositions are disclosed. The precursors have the formula: (SiH3)2N—SiH2—X, wherein X is selected from a halogen atom; an isocyanato group; an amino group; an N-containing C4-C10 saturated or unsaturated heterocycle; or an alkoxy group. Methods for forming the Si-containing film using the disclosed mono-substituted TSA precursor are also disclosed.
Despite these developments there is still a need to develop a process for forming a silicon oxide film having at least one or more of the following attributes: a density of about 1.80 g/cm3 or greater, preferably 2.0 g/cm3 or greater, most preferably 2.2 g/cm3 or greater, a growth rate of 1.5 Å/cycle or greater, preferably 2.0 Å/cycle or greater, most preferably 2.4 Å/cycle or greater, low chemical impurity, and/or high conformality in a thermal atomic layer deposition, a plasma enhanced atomic layer deposition (ALD) process or a plasma enhanced ALD-like process using cheaper, reactive, and more stable silicon precursor compounds. In addition, there is a need to develop precursors that can provide tunable films for example, ranging from silicon oxide to carbon doped silicon oxide.